JPH02175294A - Sublimable transfer recording dye - Google Patents

Abstract

PURPOSE:To control sublimable transfer amount of dye and to facilitate gradation recording by altering energy to be applied to a heat sensitive head at the time of heat transfer by using specific cyan dye. CONSTITUTION:Sublimation transfer speed relates to mutual action among dye molecules, and to mutual action between dye molecules and ink binder resin. The dye having satisfactory solubility to ink solvent and lower melting point is desired, and the dye having mutual action to the binder resin for ink to be small in the degree not lose preservation stability after a ribbon is manufactured is most desirable. Dye represented by a general formula (I) obtains relatively satisfactory sublimating speed. In the formula, R1 is cyano group, alkoxycarbonyl group, R2, R3 are lower alkyl group, alkoxy group, alkenyl group, R4 is hydrogen atom, lower alkyl group, halogen atom, etc., X is hydrogen atom, lower alkyl group, alkoxy group, and Y is hydrogen atom, lower alkyl group, alkylcarbonylamino group, halogen atom, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a cyan sublimation transfer recording dye having the general formula (1) [wherein R1 represents a cyano group or an alkoxycarbonyl group, Rt, lh represents a lower alkyl group, an alkoxyalkyl group, or an alkenyl group; R4 represents a hydrogen atom, a lower alkyl group, an alkoxy group, or a halogen atom; X represents a hydrogen atom, a lower alkyl group, or an alkoxy group; Y represents a hydrogen atom; A sublimation transfer recording dye represented by ] representing a lower alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkylsulfonylamino group, a formylamino group, or a halogen atom.

3. Detailed description of the invention [In the formula, R represents a cyano group or an alkoxycarbonyl group, R2 and R3 represent a lower alkyl group, an alkoxyalkyl group, or an alkenyl group, and R1 represents a hydrogen atom, a lower alkyl group, or an alkoxy group, a halogen atom; The present invention provides a compound represented by the following.

[Problem B to be solved by the conventional technology and invention] Thermal transfer method using sublimation dye applies sublimation dye in the form of ink to a thin condenser paper or PET film several microns thick, and selects this with a thermal head. This is one of the thermal transfer printing methods in which the image is heated and transferred onto recording paper, and is currently used as a means for recording (hard copy) various types of image information.

The sublimable dye used here has a wide range of colors, excellent color mixing properties, strong dyeing power, and relatively high stability, but the amount of sublimated dye depends on thermal energy.
In that the fourth degree after dyeing can be controlled analogously,
It has great characteristics not found in other printing methods.

However, there are very few dyes that have been proposed so far that satisfy all the conditions such as heat resistance, light resistance, sublimation speed, hue, ribbon stability, etc., and it is difficult to find a dye that satisfies the optimal conditions as a sublimable dye. has been expected.

c! Means for Solving IN) As a result of intensive studies to solve the above problems, the present inventors discovered a compound represented by the general formula (1) and completed the present invention.

That is, the present invention relates to the general formula ([) [wherein, R1 represents a cyano group or an alkoxycarbonyl group, R1 and R3 represent a lower alkyl group, an alkoxyalkyl group, or an alkenyl group, and R4 represents a hydrogen atom or a lower alkyl group] , an alkoxy group, a halogen atom, X represents a hydrogen atom, a lower alkyl group, an alkoxy group, Y represents a hydrogen atom, a lower alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkylsulfonylamino group, a formylamino group, a halogen This is a sublimation transfer recording dye represented by ], which indicates an atom.

The present invention will be explained in detail below.

In the present invention, R1 may be a cyano group or an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group.

R8 and R3 are lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and ter-butyl group, and alkoxy groups such as methoxymethyl group, ethoxymethyl group, methoxyethyl group, and ethoxyethyl group. Examples include alkenyl groups such as an alkyl group, an allyl group, a propenyl group, and a butenyl group.

Examples of R4 include a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, and a propyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, and a halogen atom such as a fluorine atom and a chlorine atom.

X is a hydrogen atom, or a methyl group, an ethyl group, a propyl group,
Lower alkyl groups such as isopropyl group, butyl group, isobutyl group, tar-butyl group, methoxy group, ethoxy group,
Examples include alkoxy groups such as propoxy groups.

Y is a hydrogen atom, or a lower alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, an alkylcarbonylamino group such as a methylcarbonylamino group, an ethylcarbonylamino group, or a propylcarbonylamino group, or methylsulfonyl. Examples thereof include an amino group, an alkylsulfonylamino group such as an ethylsulfonylamino group, a formylamino group, and a halogen atom such as a chlorine atom and a fluorine atom.

According to the research conducted by the present inventors, in conventional sublimation transfer dyes, the sublimation transfer speed is related to the interaction between the dye molecules and the interaction between the dye molecules and the binder resin for ink. It was discovered that there were.

In other words, the best pigment is one that has good solubility in the ink solvent and a low melting point, and the interaction with the ink binder resin is so small that it does not affect the storage stability after ribbon production. The dye represented by the general formula (1) of the present invention, which has been found to be 1, satisfies the above-mentioned conditions and has a relatively good sublimation rate.

The dye represented by the general formula (1) of the present invention is produced by a conventional method by synthesizing isoindolinimide from phthalonitrile and ammonia, reacting it with malonitrile or cyanacetic acid ester to acetylate it, and then converting it into an aniline derivative. It is obtained by reacting with

As a method for producing a thermal transfer recording ink using the dye of the present invention, the dye may be mixed with a suitable resin, solvent, etc. to prepare the recording ink. In addition, as a thermal transfer method,
An example of this method is to apply the ink obtained above onto a suitable base material to create a transfer sheet, overlap the sheet with a recording medium, and then heat and pressurize the sheet from the back side with a heat-sensitive recording head. In this way, the dye on the sheet is transferred onto the recording medium.

The resin used for adjusting the above ink may be those used in ordinary printing inks, such as rosin-based, phenol-based, xylene-based, petroleum-based, vinyl-based, polyamide-based,
Oil-based resins such as alkyd-based, nitrocellulose-based, and alkyl celluloses, or water-based resins such as maleic acid-based, acrylic acid-based, casein, shellac, and glue can be used.

In addition, solvents for ink adjustment include alcohols such as methanol, ethanol, propatool, and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene, and xylene, ethyl acetate, and butyl acetate. esters such as acetone, methyl ethyl ketone, ketones such as cyclohexanone, hydrocarbons such as ligroin, cyclohexane, kerosene, dimethylformamide, etc. can be used, but when using an aqueous resin, water or water and the above solvents can be used. It is also possible to mix and use them.

Suitable base materials for applying ink include thin paper such as condenser paper and glassine paper, and plastic films with good heat resistance such as polyester, polyamide, and polyimide. The thickness is appropriate.

Examples of recording materials include polyolefin resins such as polyethylene and polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl alcohol, polyvinyl acetate, and polyacrylic ester, and polyethylene terephthalate. , polyester resins such as polybutylene terephthalate,
From J styrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate and cellulose triacetate, polycarbonates, polysulfones, polyimides, etc. Examples include fibers, woven fabrics, films, sheets, molded products, etc.

Particularly preferred are woven fabrics, sheets or films made of polyethylene terephthalate.

In addition, in the present invention, V-type paper is coated or impregnated with acidic fine particles such as silica gel added to the resin, or paper is laminated with a resin film, or special processed paper subjected to acetylation treatment is used. By using it, good recording with excellent image stability at and under high temperatures can be achieved. It is also possible to use films of various resins or synthetic papers made from them.

Further, after the transfer recording, for example, a polyester film is hot-pressed and laminated on the transfer recording surface, thereby improving the color development of the dye and stabilizing the storage of the recording.

(Function and Effect) The cyan dye represented by the general formula (1) of the present invention can control the sublimation transfer amount of the dye by changing the energy given to the heat-sensitive hand during thermal transfer, so gradation recording is possible. Easy to use and suitable for full color recording.

Furthermore, since it is stable against heat, light, air, chemicals, etc., it does not undergo thermal decomposition during transfer recording, and the obtained recording has excellent storage stability.

In addition, since the pigment of the present invention has good solubility in existing solvents and good dispersibility in water, it is easy to prepare a uniformly dissolved or dispersed ink with high concentration, resulting in an ink with good color density. It is a highly valuable pigment that can be used to record records.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example-1 Phthalonitrile is synthesized by blowing ammonia gas into methanol in the presence of sodium methoxide to synthesize 1,3゜diiminoisoindoline, which is reacted with macomalonitrile in DMI to produce 1-imino-3-dicyanomethylene. After obtaining isoindoline and further acylating the imino group at the 1-position in propionic anhydride, the following formula ( The compound A) was synthesized, and the ink was adjusted, a transfer sheet, and a recording material were prepared as described below, and transfer recording was performed. The absorption maximum wavelength (Jsaχ) of this compound in chloroform was 640 nm.

b) Ink preparation method Pigment of the above formula (A) 3-part polybutyral resin 4,5〃Methyl ethyl ketone
46.25 toluene
46.25 nols of the pigment mixture with the above composition was mixed with paint conditioner using a glass piece.
The ink was prepared by mixing for 30 minutes.

(11) How to create a transfer sheet Using a gravure proofing machine (plate depth 30 μll), apply the following ink to a 9 μm thick polyethylene telescrate film whose back side has been heat-resistant treated so that the dry coating amount is 1.0 g #d. Apply and dry as shown.

(ij) Preparation of recording material Polyester resin 0.8 part (vy
lon 103 Toyobo Tg=47'C) EVA polymer plasticizer 0.2 parts (Elvaloy 74
1P Mitsui Polychemical T, -37°C) Amino-modified silicone 0.04 part (NiF
-857 Shin-Etsu Chemical Co., Ltd.) Epoxy modified silicone 0.04 part (KF
-103 manufactured by Shin-Etsu Chemical Co., Ltd.) Methyl ethyl ketone / toluene / cyclohexane (weight ratio 4:4:2) 9.0 parts or more were mixed, the coating liquid was adjusted, and synthetic paper (Yubo FPGll150 manufactured by Tamago Yuka Co., Ltd.) was mixed. Bar coater (RK Pr1n
Manufactured by L Coat Instruments,
Na1) was applied at a dry rate of 4.51/rd, and dried at 100° C. for 15 minutes.

(iv) Transfer recording The above-mentioned transfer sheet and the above-mentioned recording material are placed one on top of the other with their respective ink-coated surfaces and coating liquid-coated surfaces facing each other, and a thermal hand is applied from the back side of the thermal transfer sheet with a voltage of 10 V and a printing time of 4. Recording was performed under conditions of .0 milliseconds, and the color density was 2.5.
A cyan record of 0 was obtained.

The color density was measured using a densitometer model RD-514 (Filter Lanoten 58) manufactured by McHess, USA.

Color density was calculated using the following formula.

Color density - 1 part g. (io/I) 1o = intensity of reflected light from standard white reflector! = Intensity of reflected light from the test object In addition, the light resistance test of the obtained records was conducted using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) at a blank panel temperature of 63 ± 2'C, but after 40 hours There was almost no discoloration when exposed to heat, and the image stability at and under high temperatures was excellent.

In addition, the fastness was determined by the sharpness of the image and the coloring when the surface was rubbed with white paper after the recorded image was left in an atmosphere at 50°C for 48 hours, and the sharpness of the image did not change. Further, the white paper was not colored and the fastness of the recorded image was good.

Example-2 1,3-diiminoisoindoline was synthesized by blowing ammonia gas into phthalonitrile in methanol in the presence of sodium methoxide, and it was reacted with ethyl cyanacetate in DMF to produce ■-imino-3-ethoxy Carbonyl cyanomethylene isoindoline was obtained and further reacted with several drops of 4-sulfuric acid and 3-diethylamino-4-methoxyacetanilide in acetic anhydride to synthesize a compound of the following formula (B).

Maximum absorption wavelength (λt) of the compound in chloroform
aax) was 630 nm.

In the same manner as in Example 1, the ink was adjusted, a transfer sheet, and a recording material were prepared, and transfer recording was performed to obtain a cyan recording with a color quadrature of 2.50.

All of these records were subjected to a light fastness test in the same manner as in Example 1, and the records showed almost no change and were excellent in image stability under high temperature and high humidity conditions.

Further, a fastness test was conducted in the same manner as in Example 1, but the sharpness of the image did not change, the white paper did not become colored, and the fastness of the recorded image was good.

Examples 3 to 10 Cyan dyes shown in Table 1 were produced according to the same method as in Example 1, and the ink adjustment, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1. Each record shown in R-1 was obtained.

All of these records were subjected to a light fastness test in the same manner as in Example 1, and the records showed almost no change and were excellent in image stability at and under high temperatures.

In addition, during the fastness test in the same manner as in Example 1, the sharpness of the image did not change and the blank paper did not become colored.
i! The fastness of the N image was good.

(Margin below) Table-1 Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1 represents a cyano group or an alkoxycarbonyl group, and R_2 and R_3 represent a lower alkyl group or an alkoxy represents an alkyl group or an alkenyl group, R_4 represents a hydrogen atom, a lower alkyl group, an alkoxy group, or a halogen atom;
represents a hydrogen atom, a lower alkyl group, or an alkoxy group, and Y
represents a hydrogen atom, a lower alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkylsulfonylamino group, a formylamino group, or a halogen atom. ] A dye for sublimation transfer recording.